JP4975355B2 - Additives for fluorinated oils - Google Patents

Description

  The present invention relates to an additive for lubricating oils and greases that can improve the thermal stability of lubricating oils and greases in the presence of metals and in an oxidizing environment (for example, in the air), and a method for producing the same. More specifically, the present invention is a perfluoropolyether structure capable of stabilizing lubricants such as oils and greases, preferably excellent rust prevention and storage at 25 ° C. such as no phase separation. The present invention relates to an additive having a perfluoropolyether structure that can further impart excellent stability (storage stability).

Perfluoropolyethers have long been known to have good chemical and thermal stability, as lubricants and greases, and over a wide range of operating temperatures, especially in harsh operating environments such as corrosive compounds and It is known to be used as hydraulic fluid for hydraulic devices that require a wide temperature range in the environment where it comes into contact with ionizing radiation.
However, these lubricants exhibit thermal stability limits when subjected to certain critical operating conditions, for example, in an oxidizing environment (eg, in air) and in the presence of metals, at temperatures above 280 ° C. There is a drawback that it is easy to disassemble.
In the decomposition process under the above conditions, first, the perfluoropolyether chain is broken, or in some cases, the lubricant itself is decomposed, and the performance of the lubricant is deteriorated.
Furthermore, the breakdown of hydraulic oil is usually accompanied by the progress of corrosion of the metal itself.

  It has been conventionally known that the oxidation resistance of oils and greases having a perfluoropolyether structure under high temperature conditions in the presence of a metal can be improved by using a specific stabilizer. Stabilizers are required to have good compatibility with perfluoropolyether oil. Stabilizers containing phosphorus and fluorine substituents are known.

Patent Document 1 describes a stabilizer for a perfluoropolyether lubricant having a main chain in which an aryl phosphine unit or a derivative thereof is bonded to a perfluoropolyether chain via oxygen or sulfur element. This compound is produced in a multi-step process involving intermediate products that are difficult to produce. Therefore, this manufacturing process is difficult to use industrially.
Patent Document 2 discloses a phosphazene derivative-based stabilizer for a perfluoropolyether lubricant having both an aromatic group and a (per) fluoropolyether chain in the phosphazene ring. The method of synthesizing stabilizers is not selective and cannot reliably obtain an additive having a defined chemical structure. Furthermore, phosphazene precursors are expensive and disadvantageous from an industrial point of view. Applicants' tests have shown that these compounds have poor storage stability.
U.S. Pat. No. 4,681,693 European Patent No. 597,369

Patent Document 3 describes perfluoropolyether phosphotolyazines as stabilizers for perfluoropolyether oils. This derivative requires many steps to produce it, and materials that are difficult to produce, such as perfluorinated epoxides, are required.
Patent Document 4 discloses a stabilizer for a perfluoropolyether lubricant having a structure of a phosphate substituted with an aromatic phosphate or perfluoropolyether. This synthesis method is very complicated and requires many steps, and an organic metal material such as butyl lithium, which is known to be difficult to use industrially in terms of safety, must be used.
US Pat. No. 5,326,910 US Pat. No. 5,550,277

Patent Document 5 discloses a phosphate ester typified by aryl phosphates in which at least one perfluoropolyether chain is substituted. Aromatic chlorinated esters are used for the production of this additive. This compound has the disadvantage of being very expensive. Furthermore, as shown in the Examples of this publication, phosphate esters are obtained by reaction of aromatic alcohols with POCl ₃ . POCl ₃ is a toxic and easily damaged chemical compound and requires special equipment for use in industrial hope.
International Publication WO99 / 51,612

  The above-mentioned stabilizer containing phosphorus has an excellent stabilizing effect, but the production method for obtaining this stabilizer requires the use of raw materials that are expensive and difficult to produce, and on an industrial scale. It has difficult technical problems and operational conditions that must be solved for production. In addition, some of these stabilizers have the disadvantage of low storage stability.

Known stabilizers for use in perfluoropolyether lubricants do not contain phosphorus.
For example, Patent Document 6 discloses an oligomer having a perfluoroalkylene ether-triazine structure as a lubricant exhibiting an excellent stabilizing effect against oxidation in the presence of a metal. This oligomer can also be used as a stabilizer for oils and greases having a perfluoropolyether structure. However, the method for producing the stabilizer requires a process that requires the use of a precursor that is difficult to produce, and the yield is less than 40%, which is disadvantageous from an economic viewpoint. There is nothing to say about the antirust properties of this compound.
Patent Document 7 filed by the present applicant discloses a stabilizer having a perfluoropolyether structure not containing phosphorus and having an aryl terminal group containing a NO ₂ group. This stabilizer is used to stabilize perfluoropolyether oils and greases in a thermally oxidative environment in the presence of metals. According to the applicant's test results, although this stabilizer is excellent in stabilizing effect, it has a problem of causing phase separation at room temperature. As a result, the composition containing this stabilizer has insufficient storage stability.
US Pat. No. 5,942,598 European Patent 1,354,932

In the above situation, fluorinated lubricants, especially lubricants having a perfluoropolyether structure, can be stabilized at high temperatures in the presence of oxidizing environments and metals, exhibiting rust prevention effects, and fluorinated at room temperature There is a need for stabilizers in which lubricating oils and greases are stable without phase separation, and the resulting composition has storage stability and can be produced by a simple industrial process.
The Applicant has found that certain compounds having a perfluoropolyether structure can surprisingly and surprisingly satisfy all of the above properties.

  The object of the present invention is a compound represented by formula (I) having at least one aryl triazine end group and containing a perfluoropolyether chain.

〔Ｒ_ｆは、（ＣＦＸＯ）、（ＣＦ_２ＣＦ_２Ｏ）、（ＣＦ_２ＣＦ_２ＣＦ_２Ｏ）、（ＣＦ_２ＣＦ_２ＣＦ_２ＣＦ_２Ｏ）、（ＣＲ_６Ｒ_７ＣＦ_２ＣＦ_２Ｏ）、（ＣＦ（ＣＦ_３）ＣＦ_２Ｏ）、（ＣＦ_２ＣＦ（ＣＦ_３）Ｏ） ｛ただし、Ｘ＝Ｆ，ＣＦ_３； Ｒ_６及びＲ_７は、Ｈ、Ｃｌ、又は炭素数１〜４のパーフルオロアルキルから選択されるもので同じでも又は互いに異なってもよい。｝ の構造を有する１又は２以上の繰り返し単位を主鎖に統計学的確率で有する、（パー）フルオロポリオキシアルキレン鎖であり、Ｒ_ｆの数平均分子量が５００〜１０，０００、好ましくは５００〜５，０００であり；
Ｗ_１及びＷ_２は、−Ｆ、又は−ＣＦ_３であり、同じであっても又は互いに異なってもよく；
Ｔ_１は、−ＣＨＡ_ａ−Ｂ_ａ（ＣＨ_２ＣＨ_２Ｏ）_na− ｛但し、Ａ_ａ＝Ｈ、ＣＦ_３；Ｂ_ａ＝Ｏ、Ｓ、ＮＨ；ｎａは０〜６の整数で両端が含まれる。｝であり；
Ｔ_２は、−Ｆ、−ＣＦ_３、−Ｃ_２Ｆ_５、−（Ｃ_２Ｆ_４）Ｃｌ、又は

_[R f _{is, (CFXO), (CF 2} CF 2 O), (CF 2 CF 2 CF 2 O), (CF 2 CF 2 CF 2 CF 2 O), (CR 6 R 7 CF 2 CF 2 O) , (CF (CF ₃ ) CF ₂ O), (CF ₂ CF (CF ₃ ) O) (where X = F, CF ₃ ; R ₆ and R ₇ are H, Cl, or C 1-4, They are selected from perfluoroalkyl and may be the same or different from each other. } A (per) fluoropolyoxyalkylene chain having 1 or 2 or more repeating units having the following structure in the main chain with a statistical probability, and the number average molecular weight of R _f is 500 to 10,000, preferably 500 ~ 5,000;
W ₁ and W ₂ are —F or —CF ₃ and may be the same or different from each other;
T ₁ is —CHA _a —B _a (CH ₂ CH ₂ O) _na — {where A _a = H, CF ₃ ; B _a = O, S, NH; na is an integer of 0 to 6 and includes both ends. It is. };
T ₂ is —F, —CF ₃ , —C ₂ F ₅ , — (C ₂ F ₄ ) Cl, or

で示される基であり；
Ｑ_１及びＱ_２は、−Ｔ_１−ＣＦＷ_１−Ｏ−Ｒ_ｆ−ＣＦＷ_２−Ｔ^’ _２の構造のパーフルオロオキシアルキレン鎖 ｛Ｔ^’ _２は、−Ｆ、−ＣＦ_３、−Ｃ_２Ｆ_５、−（Ｃ_２Ｆ_４）Ｃｌである。；Ｔ_１、Ｗ_１及びＷ_２は、上記と同じ意味である。｝、又は

A group represented by:
Q ₁ and Q ₂ are each a perfluorooxyalkylene chain having a structure of —T ₁ —CFW ₁ —O—R _f —CFW ₂ —T ^′ ₂ {T ^′ ₂ is —F, —CF ₃ , —C ₂ F _{5, -} a _{(C 2} F 4) Cl. T ₁ , W ₁ and W ₂ have the same meaning as above. }, Or

で示される基｛ＢはＯ、Ｓ、ＮＨであり；Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５は、Ｈ、Ｆ、ＮＯ_２、ＣＮ、直鎖の又は分岐したＣ_１〜Ｃ_８のパーフルオロアルキル、カルボキシル、フェニル（Ｐｈ）、Ｏ−Ｐｈ、ＮＨ−Ｐｈ、Ｓ−Ｐｈから選ばれるものであり、同じであっても又は互いに異なってもよい。｝であり、Ｑ_１及びＱ_２は、同じでも又は相互に異なっていてもよい。
但し、Ｑ_１とＱ_２は少なくとも一つが、

A group represented by {B is O, S, NH; R ₁ , R ₂ , R ₃ , R ₄ , R ₅ are H, F, NO ₂ , CN, linear or branched C ₁ -C ₈ perfluoroalkyl, carboxyl, phenyl (Ph), O-Ph, NH-Ph, S-Ph, which may be the same or different from each other. }, And Q ₁ and Q ₂ may be the same or different from each other.
However, _{Q 1} and _{Q 2} are at least one of,

で示される基である。〕

It is group shown by these. ]

Preferred perfluoropolyether chains _Rf are those selected from the structures of formulas (A) to (F).
(A)
_{- (CF 2 CF (CF 3} ) O) a (CFXO) b -
Or _{- (CF 2 CF (CF 3} ) O) a (CFXO) b -CF 2 (R 'f) CF 2 -O- (CF 2 CF (CF 3) O) a (CFXO) b -
{In the formula (A), R _^'f is fluoro alkylene group having 1 to 4 carbon atoms; X is F or CF _3; a and b is an integer number average molecular weight is in the above range; a / b is between 10 and 100 and b is not 0. };

(B)
_{- (CF 2 CF 2 O)} c (CF 2 O) d (CF 2 (CF 2) z O) h -
{In formula (B), c, d and h are integers whose number average molecular weight is within the above range; c / d (d is not 0) is between 0.1 and 10; h / (c + d) ((c + d) is not 0) is between 0 and 0.05; z is 2 or 3; h may be 0. };

(C)
_{- (CF 2 CF (CF 3} ) O) e (CF 2 CF 2 O) f (CFXO) g -
{In Formula (C), X is F or CF ₃ ; e, f, g are integers whose number average molecular weight is within the above range; e / (f + g) is between 0.1 and 10 ; (F + g) is not 0: f / g is between 2 and 10. };

(D)
− (CF ₂ (CF ₂ ) _z O) _s −
{In formula (D), s is an integer that gives the molecular weight, and z has the meaning already defined. };

(E)
− (CR ₆ R ₇ CF ₂ CF ₂ O) _{j ′} −
Or _{- (CR 6 R 7 CF 2} CF 2 O) p '-R' f -O- (CR 6 R 7 CF 2 CF 2 O) q '-
{Wherein in (E), _{R 6} and _{R 7} are H, Cl, or selected from perfluoroalkyl having 1 to 4 carbon atoms, same or may be different from each other; R _^'f is from 1 to 4 carbon atoms And j ^′ , p ^′ , and q ^′ are integers having the above molecular weight. };

(F)
− (CF (CF ₃ ) CF ₂ O) _{j ″} −
{J ^″ in the formula (F) is an integer that gives the molecular weight.}

More preferable R _f in the compound represented by the formula (I) is selected from the structures of the formula (A) and the formula (B).

  The applicant has surprisingly and surprisingly used the compounds of the present invention as additives for perfluoro-based lubricants such as perfluoropolyether oils and perfluoropolyether greases, It has been found that the thermal stability of the lubricant is improved in an oxidizing environment and in the presence of a metal, and also exhibits excellent rust prevention properties and excellent storage stability at 25 ° C.

Perfluoropolyether compounds having at least one aryl triazine end group are transparent, odorless and highly viscous liquids.
A further subject of the present invention is a 99.95-90% by weight, preferably 99.5-95% by weight perfluoropolyether oil or PFPE-based grease based on perfluoropolyether oil, and 0.05-10 Lubricant composition containing at least one triazine compound of the structure of formula (1), by weight%, preferably 0.5-5% by weight.

Examples of perfluoropolyether oils include those selected from the classifications of formulas (1) to (8).
(1)
_{E-O- [CF 2 CF (} CF 3) O] m '(CFXO) n' -E '
[In the formula (1), X is —F or —CF ₃ ; E and E ^′ are selected from —CF ₃ , —C ₂ F ₅ or —C ₃ F ₇ and are the same or different from each other. M ^′ and n ^′ have a ratio of m ^′ / n ^′ between 20 and 1000, n ^′ is not 0; and a viscosity at 20 ° C. between 10 cSt and 4,000 cSt. The repeating units are distributed with statistical probability in the main chain. ]
This polymer undergoes a photo-oxidation reaction of perfluoropropene as disclosed in British Patent GB 1,104,432, and then a terminal group substitution reaction as disclosed in British Patent GB 1,226,566. Can be obtained by doing.

(2)
_{C 3 F 7 O- [CF (} CF 3) CF 2 O] o '-D
[In the formula (2), D is an _-C 2 _{F 5} or _-C 3 _{F 7;} o ^'is an integer such that the viscosity of the product is within the above reported range under (1). ]
This polymer can be obtained by performing ion oligomerization of perfluoropropylene oxide as disclosed in US Pat. No. 3,242,218, followed by treatment with fluorine.

(3)
_{{C 3 F 7 O- [CF} (CF 3) CF 2 O] p '-CF (CF 3) -} 2
[In formula (3), p ^′ is an integer whose viscosity falls within the range described in formula (1). ]
This material can be obtained by ion telomerization of perfluoropropylene oxide as reported in U.S. Pat. No. 3,214,478 followed by a photochemical dimerization reaction.

(4)
_{E-O- [CF 2 CF (} CF 3) O] q '(C 2 F 4 O) r' (CFX) s '-E'
[In the formula (4), X is —F or —CF ₃ ; E and E ^′ are selected from —CF ₃ , —C ₂ F ₅ or —C ₃ F ₇ and may be the same or different from each other; q ^′ , r ^′ and s ^′ are integers (including 0) whose viscosity falls within the range described in the formula (1). ]
This polymer is obtained by performing a photo-oxidation reaction of a mixture of C ₃ F ₆ and C ₂ F ₄ as disclosed in US Pat. No. 3,665,041, and then treating with fluorine. Can do.

(5)
_{E-O- (C 2 F 4} O) t '(CF 2 O) u' -E '
[In formula (5), E and E ^′ are selected from —CF ₃ , —C ₂ F ₅ or —C ₃ F ₇ and may be the same or different from each other; t ^′ and u ^′ are t ^′ / ^'it is between the ratio of 0.1 and 5, ^u' u is not zero, and the viscosity is an integer comprised within the range according to equation (1). ]
This polymer performs a photo-oxidation reaction of C ₂ F ₄ as reported in US Pat. No. 3,715,378 and then uses fluorine as disclosed in US Pat. No. 3,665,041. It can be obtained by performing the processing.

(6)
_{E-O- (CF 2 CF 2} CF 2 O) v '-E'
[In formula (6), E and E ^′ are selected from —CF ₃ , —C ₂ F ₅ or —C ₃ F ₇ and may be the same or different from each other; v ^′ may have a viscosity of formula (1) The number falls within the range described in. ]
This polymer can be obtained as reported in EP 148,482.

(7)
_{D-O- (CF 2 CF 2} O) z '-D'
[D and D ^′ in the formula (7) are selected from —C ₂ F ₅ or —C ₃ F ₇ and may be the same or different from each other; z ^′ is the range described in the formula (1) An integer that is inside. ]
This polymer can be obtained as reported in US Pat. No. 4,523,039.

(8)
_{E 1 -O (CF 2 O)} n (CF 2 CF 2 O) m - (CF 2 CF 2 CF 2 O) p (CF 2 CF 2 CF 2 CF 2 O) q -E 2
[In Formula (8), E ₁ and E ₂ are perfluoroalkyl end groups having a structure of — (CF ₂ ) _z CF ₃ , and z is an integer of 0 to 3, which may be the same or different from each other. N, m, p, q are integers whose viscosities fall within the range described in formula (1), m / n is between 2 and 20, preferably between 2 and 10, n is not 0; the ratio of (p + q) / (m + n + p + q) is between 0.05 and 0.2, (m + n + p + q) is not 0; n / (m + n + q + p) is 0.05 and 0.4 (M + n + p + q) is not 0. ]
This material is obtained according to EP 1,454,938.

  Suitable perfluoropolyether oils are those of any of the above formulas (1), (4), (5) and (8).

The perfluoropolyethers of the class of formulas (1) to (8) having perfluoroalkyl end groups are liquids having a very low vapor pressure, and the viscosity at 20 ° C. is usually 10 cSt. A liquid between 100,000 cSt, preferably between 40 cSt and 2,000 cSt.
The perfluoropolyether that can be used to produce oils or greases may be a commercial product as exemplified by FOMBLIN (Solvay Solex: registered trademark).

The lubricant composition of the present invention has high storage stability at room temperature and does not observe substantial phase separation even after a long period of time.
The compositions of the present invention can contain other additives commonly used in perfluoropolyether lubricants, such as antiwear agents.

  A further subject of the present invention is a method for producing a triazine compound of formula (1) comprising the following production steps:

Production stage A:
(I)
Perfluoropolyoxyalkylene derivative T ^″ ₁ -CFW ₁ —O—R _f —CFW ₂ —T ^” ₂ (II) represented by the formula (II)
_[R f, _{W 1} and _{W 2} is the same meaning as ^{above; T} _"1 and _{^T" 2} are same or different from each other which may be -CHA _a -B _a of _{(CH 2 CH 2 O) na} -H Having structure {A _a = H, CF ₃ ; B _a = O, S, NH; na is an integer of 0 to 6 and includes a terminal. Or selected from F, CF ₃ , C ₂ F ₅ , (C ₂ F ₄ ) Cl; provided that at least one of the two terminals T ^″ ₁ and T ^″ ₂ is —CHA _a —B _a a _{(CH 2 CH 2 O) na} -H, _preferably selected from _{O-CH 2 OH, O-} CH 2 SH, O-CH 2 NH 2, CH (OH) CF 3. 〕When,

式（ＩＩＩ）で示されるトリハロトリアジン〔Ｊ＝Ｃｌ、Ｆ、好ましくはＣｌ〕とを、
０℃と１０℃との間の温度で、反応物を溶解可能な該反応条件において不活性な溶媒と、有機塩基又は無機塩基との存在下で、式（ＩＩ）で表される化合物の当量数と式（ＩＩＩ）で表される化合物のモル数との比が１：１で、好ましくは攪拌しながら、反応させ、

A trihalotriazine of formula (III) [J = Cl, F, preferably Cl],
Equivalents of the compound of formula (II) in the presence of a solvent inert to the reaction conditions capable of dissolving the reactants at a temperature between 0 ° C. and 10 ° C. and an organic or inorganic base The ratio of the number to the number of moles of the compound represented by formula (III) is 1: 1, preferably with stirring, the reaction

(Ii)
The reaction product obtained in the above (i) and the compound represented by the formula (IV) are represented by QH (IV)
[Q is Q ₁ and Q ₂ described above. ]
React in a temperature range of 25-35 ° C.,

(Iii)
The reaction product obtained in the above (ii) and the compound represented by the formula (IV) (which may be the same as or different from those used in the above (ii)) may be 65 to 100 ° C., preferably The reaction is carried out in the temperature range of 70-90 ° C.

Production stage B:
The organic phase of the reaction mixture obtained in production stage A is separated from the aqueous phase, and then the remaining organic or inorganic insoluble salt is separated off from the organic phase, preferably by a filter.

Production stage C:
The organic phase is washed several times with an aqueous acid solution and then the compound of formula (I) is separated from the organic solvent, for example by evaporation.

  The inert solvent in the production stage A is preferably selected from toluene, xylene, hexafluoroxylene, acetone, diethyl ketone and the like. The amount of solvent used depends on the solubility of the reactants in the solvent.

NaOH, KOH, Na ₂ CO ₃ , K ₂ CO ₃ can be used as the inorganic base in stage A.
As the organic base, 2,6-dimethylpyridine, 2-methylquinoline, 2,4,6-trimethylpyridine (collidine) can be used. As a suitable base, 2,4,6-trimethylpyridine is used.

The ratio of the number of equivalents of base to the sum of the number of equivalents of compounds of formula (II) and formula (IV) used in the three steps of stage A is 1: 1 to 2: 1, preferably 1 : 1 to 1.5: 1.
The reaction time in each step is between 2 and 8 hours, preferably between 4 and 6 hours.

  The compound represented by the formula (II) is a known substance disclosed in, for example, US Pat. No. 6,509,509 and US Pat. No. 5,124,058. Substances represented by the formulas (III) and (IV) are known substances and can be obtained as commercial products.

By the production method of the present invention, only one halogen atom of the triazine ring (III) can be selectively substituted. That is, by performing steps i), ii) and iii) of production stage A, a highly selective substitution reaction of the halogen atom of triazine compound (III) occurs, and an additive having a predetermined chemical structure is obtained. be able to.
By the production method in which this selective reaction occurs, the triazine compound represented by the formula (I) can be obtained in a yield exceeding about 90%.

As described above, the additive of the present invention does not contain phosphorus. And this invention additive with the chemical structure defined by the manufacturing method which shows simple and high selectivity can be obtained with a high yield.
By using this additive, it is possible to expand the range in which perfluoropolyether lubricants can be used in a thermally oxidative environment in the presence of metals, particularly at temperatures in excess of 280 ° C. Furthermore, the additive of the present invention is excellent in rust prevention and storage stability at 25 ° C.

The lubricant composition containing the additive of the present invention does not cause a substantial reduction in the lubrication effect in the presence of metals and in a high temperature oxidizing environment exceeding 200 degrees (in the presence of air or oxygen). It can be used. In particular, the lubricant composition containing the additive of the present invention can be used even at a temperature of about 300 ° C.
Furthermore, the composition of the present invention has an advantageous effect of being stable even during long-term storage at room temperature, and overcomes the drawbacks of the prior art.

The Applicant has surprisingly and surprisingly been able to disperse the fluorinated oils at room temperature despite the fact that the compounds of the present invention contain non-fluorinated substituents such as phenolic groups, It was found that phase separation did not substantially occur and the storage stability was excellent.
As described above, the additive of the present invention can be used in lubricating oils and greases, preferably in fluorine-based greases, and particularly preferably in perfluoropolyether-based greases.

When used in perfluoropolyether-based lubricating greases, the lubricant composition can be used as a basic component in addition to the additive of the present invention and the perfluoropolyether oil belonging to one or more of the above classes. The amount of thickener used in 1), for example, PTFE, sodium terephthalamidate (sodium terephthalate), calcium or lithium soaps, polyurea and the like.
In addition, the lubricant composition may also contain other additives commonly used in the grease art, such as talc, inorganic fillers, antiwear agents.
When PTFE is used as the thickener, the primary particle size of the PTFE polymer measured with a scanning electron microscope (SEM) is between 0.02 μm and 0.25 μm. The particles can be obtained by a known method such as a microemulsion polymerization method, an emulsion polymerization method, or a suspension polymerization method.

  The invention is explained in more detail by showing the following examples. However, these examples are merely illustrative and the present invention is not limited thereto.

(Evaluation method)
Micro oxidation test using equipment described in non-patent literature (Carl E. Snyder, Jr. and Ronald E. Dolle, Jr., ASLE Transactions, 13 (3), 171-180 (1975)) A test was conducted.
The operating conditions are as follows.
Test temperature: 300 ° C
Air flow rate: 1 l / h
Metal immersed in liquid: stainless steel (AISI 304) and titanium alloy (Al 6%, V 4%)
Test time: 24 hours, 48 hours, 72 hours The lubricant composition used for the test is poured into the glass test tube of the apparatus shown in FIG. 1 of the literature, and the metal is immersed in the lubricant composition. The mass of the entire glass test tube containing the lubricant composition and metal was measured and heated to the test temperature. When 24 hours, 48 hours and 72 hours have elapsed, the glass test tubes are cooled to room temperature and weighed again. From the difference in mass before and after heating, the percentage of weight loss of the test composition is determined. After the test, the state of the surface of the metal immersed in the lubricant composition is observed and evaluated.

Spray test (rust prevention)
A carbon steel (C15) (UNI) sheet having a size of 50 × 100 × 2 mm is polished with 400-800 mesh sandpaper, washed with a cloth soaked with n-hexane, degreased and dried.
The sheet was dip coated with the dispersion under test and then placed in a nebulizer. The nebulizer is composed of one spray and a water supply connected thereto, and the air in the nebulizer at 35 ° C. can be saturated with water vapor by compressing air to 3 atm. The sheet is left in the nebulizer, sealed, saturated with water vapor, and regularly observed to see if the surface is soiled.
The result of this spray test was evaluated according to the following classification.
(0) No rust stains;
(1) 1 to 3 corrosion points less than 1 mm in diameter (2) 3 soils with a diameter greater than 1 mm, or a percentage of corroded surfaces with many soils with a diameter less than 1 mm less than 1%;
(3) 4 or 5 soils with a diameter greater than 1 mm, or a percentage of corroded surfaces with many soils with a diameter less than 1 mm between 1% and 5%;
(4) Corroded surface percentage between 5% and 10%;
(5) The proportion of the corroded surface exceeds 10%.

The kinematic viscosity and kinematic viscosity of the perfluoropolyether oil was measured by a capillary viscometer Cannon-Fenske according to ASTM D445 method.

(Manufacture of additives)
Example 1 (Production of Additive (I) shown in Chemical Formula 6)

[C and d are integers such that c / d = 2 and the average molecular weight of OCH ₂ CF ₂ (OCF ₂ ) _d (OCF ₂ CF ₂ ) _c OCF ₂ CH ₂ O is 1,464. ]

300 g of hexafluoroxylene, 12.7 g (0.068 mol) of 2,4,6-trichlorotriazine, and 9 g (0.074 mol) of collidine were added to a 1 L glass flask equipped with a stirrer, a temperature controller and a dropping funnel. Prepare. The reaction mixture was cooled to 0 ° C., the temperature in the flask was maintained between 0 ° C. and 10 ° C., and HOCH ₂ CF ₂ (OCF ₂ ) _d (OCF ₂ CF ₂ ) having a molecular weight of 1,466 was stirred. ) _C OCF ₂ CH ₂ OH 50 g (0.034 mol, 0.068 eq) is slowly added dropwise.
The state is maintained for about 2 hours after the dropping of alcohol is completed. The reaction mixture is then returned to room temperature and maintained in this state for a further 2 hours.

9 g (0.074 mol) of collidine is added and the temperature is brought to 30 degrees. Under this condition, 42.8 g (0.068 equivalent) of Cl (C ₃ F ₆ O) _a CF ₂ OH having a molecular weight of 631 is added dropwise with stirring. After completion of the addition, the reaction is allowed to proceed for about 4 hours with stirring. An additional 9 g (0.074 mol) of collidine and 6.4 g (0.068 equivalents) of phenol are added to the reaction mixture. After the addition, the temperature is raised to 80 ° C. and allowed to react in that state for about 6 hours.
Cool and remove the precipitate of collidine hydrochloride from the reaction mixture by filtration.
The organic liquid is washed with 150 g of hydrochloric acid having a concentration of 2% by weight, the organic phase is separated, the solvent is evaporated, and the product is rectified at 130 ° C./1 mmHg for 4 hours. 96.3 g of product are obtained with a yield of 92%. Analysis by IR and NMR ( ¹ H, ¹³ C, and ¹⁹ F) confirmed the structure of the product and confirmed that it was synthesized with high selectivity.

Example 2 (Production of Additive (I) shown in Chemical Formula 7)

［ｃ及びｄはｃ／ｄ＝２となり且つＯＣＨ_２ＣＦ_２（ＯＣＦ_２）_ｄ（ＯＣＦ_２ＣＦ_２）_ｃＯＣＦ_２ＣＨ_２Ｏ の平均分子量が１，４６４となる整数である。］

[C and d are integers such that c / d = 2 and the average molecular weight of OCH ₂ CF ₂ (OCF ₂ ) _d (OCF ₂ CF ₂ ) _c OCF ₂ CH ₂ O is 1,464. ]

The same procedure as in Example 1 was carried out except that 9.4 g (0.068 equivalent) of p-nitrophenol was used instead of phenol.
97.8 g of product are obtained with a yield of 91%. Analysis by IR and NMR ( ¹ H, ¹³ C, and ¹⁹ F) confirmed the structure of the product and confirmed that it was synthesized with high selectivity.

Example 3 (Production of additive shown in Chemical formula 8)

[A is an integer such that the number average molecular weight of T ^′ ₁ -CFW ₁ -O (C ₃ F ₆ O) _a -CFW ₂ -T ^′ ₂ is 3770; W ₁ and W ₂ are F or CF ₃ T ^′ ₁ is —F, —CF ₃ , —C ₂ F ₅ ; T ^′ ₂ is —CH (CF ₃ ) O— and —CH ₂ —O— at a ratio of 60/40. ]

300 g of hexafluoroxylene, 6.35 g (0.034 mol) of 2,4,6-trichlorotriazine, and 4.5 g (0.036 mol) of collidine were added to a 1 L glass equipped with a stirrer, a temperature controller and a dropping funnel. Charge into a flask.
The reaction mixture was cooled to 0 ° C., the temperature in the flask was maintained between 0 ° C. and 10 ° C., and while stirring, compound (II) having a molecular weight of 3,771: T ^′ ₁ -CFW ₁ —O ( _{C 3 F 6 O) a -CFW} 2 -T ' slowly added dropwise ₂ -H 128 g (0.034 mol). Compound (II) is produced according to the method described in US Pat. No. 5,124,058.

The state is maintained for about 2 hours after the dropping of alcohol is completed. The reaction mixture is then returned to room temperature and maintained in this state for a further 2 hours.
9 g (0.074 mol) collidine and 9.4 g (0.068 equivalents) p-nitrophenol are added. After the addition, the temperature is raised to 80 ° C. and allowed to react in that state for about 6 hours.
Cool and remove the precipitate of collidine hydrochloride from the reaction mixture by filtration.
The organic liquid is washed with 150 g of hydrochloric acid having a concentration of 2% by weight, the organic phase is separated, the solvent is evaporated, and the product is rectified at 130 ° C./1 mmHg for 4 hours. 133 g of product are obtained with a yield of 95%. Analysis by IR and NMR ( ¹ H, ¹³ C, and ¹⁹ F) confirmed the structure of the product and confirmed that it was synthesized with high selectivity.

Example 4 (Production of additive shown in Chemical formula 9)

[A is an integer such that the number average molecular weight of T ^′ ₁ -CFW ₁ -O (C ₃ F ₆ O) _a -CFW ₂ -T ^′ ₂ is 1295; W ₁ and W ₂ are F or CF ₃ ; _{^'1 -F,} -CF 3, is _{-C 2 F 5;} ^T' 2 is -CH _(CF 3) at a ratio of 60/40 is O and _-CH 2 -O. ]

300 g of hexafluoroxylene, 7.1 g (0.038 mol) of 2,4,6-trichlorotriazine, and 5 g (0.041 mol) of collidine were added to a 1 L glass flask equipped with a stirrer, a temperature controller and a dropping funnel. Prepare.
The reaction mixture was cooled to 0 ° C., the temperature in the flask was maintained between 0 ° C. and 10 ° C., and the compound (II) having a molecular weight of 1,296: T ^′ ₁ -CFW ₁ —O ( _{C 3 F 6 O) a -CFW} 2 -T '2 -H 50g (0.038 mol) is slowly added dropwise. Compound (II) is produced according to the method described in US Pat. No. 5,124,058.
The state is maintained for about 2 hours after the dropping of alcohol is completed. The reaction mixture is then returned to room temperature and maintained in this state for a further 2 hours.

Add 5 g (0.041 mol) collidine and bring the temperature to 30 degrees. Under this condition, 50 g (0.038 equivalent) of T ^′ ₁ -CFW ₁ —O (C ₃ F ₆ O) _a —CFW ₂ —T ^′ ₂ —H is added dropwise with stirring. After completion of the addition, this state is allowed to react for about 4 hours with stirring.
An additional 5 g (0.041 mol) of collidine and 3.6 g (0.088 equivalents) of phenol are added. After the addition, the temperature is raised to 80 ° C. and allowed to react in that state for about 6 hours.
Cool and remove the precipitate of collidine hydrochloride from the reaction mixture by filtration.
The organic liquid is washed with 150 g of hydrochloric acid having a concentration of 2% by weight, the organic phase is separated, the solvent is evaporated, and the product is rectified at 130 ° C./1 mmHg for 4 hours. 98.2 g of product are obtained with a yield of 92%. Analysis by IR and NMR ( ¹ H, ¹³ C, and ¹⁹ F) confirmed the structure of the product and confirmed that it was synthesized with high selectivity.

Example 5 (Comparative Example: Production of triazine additive containing no aryl substituent as shown in Chemical Formula 10)

[A is an integer such that the number average molecular weight of T ^′ ₁ -CFW ₁ -O (C ₃ F ₆ O) _a -CFW ₂ -T ^′ ₂ is 3770; W ₁ and W ₂ are F or CF ₃ ; _{^'1 -F,} -CF 3, in some _-C 2 _{F 5;} ^T' is ₂ -CH _(CF 3) at a ratio of 60/40 O-and is _-CH 2 -O-. ]

300 g of hexafluoroxylene, 6.35 g (0.034 mol) of 2,4,6-trichlorotriazine, and 13.5 g (0.108 mol) of collidine were added to a 1 L glass equipped with a stirrer, a temperature controller and a dropping funnel. Charge into a flask.
The reaction mixture was cooled to 0 ° C., the temperature in the flask was maintained between 0 ° C. and 10 ° C., and while stirring, compound (II) having a molecular weight of 3,771: T ^′ ₁ -CFW ₁ —O ( _{C 3 F 6 O) a -CFW} 2 -T ' slowly added dropwise ₂ -H 384 g (0.102 mol).

After completing the dropping of the alcohol, the temperature is slowly raised to 80 ° C. and the reaction is continued for about 6 hours.
Cool and remove the precipitate of collidine hydrochloride from the reaction mixture by filtration.
The organic liquid is washed with 150 g of hydrochloric acid having a concentration of 2% by weight, the organic phase is separated, the solvent is evaporated, and the product is rectified at 130 ° C./1 mmHg for 4 hours. 370 g of product are obtained with a yield of 93%. Analysis by IR and NMR ( ¹ H, ¹³ C, and ¹⁹ F) confirmed the structure of the product and confirmed that it was synthesized with high selectivity.

(Application evaluation)
Example 6
0.5 g of the additive obtained in Example 4 was added to 50 g of a perfluoropolyether oil belonging to the classification (5) having a kinematic viscosity at 20 ° C. of 260 cSt (commercial product: Fomblin (registered trademark) Z25). Place in a glass test tube for metal micro oxidation test. After 24 hours at 300 ° C. under the above micro-oxidation test conditions, a weight loss of 1.1% by weight occurred.
Metals (stainless steel and Ti, Al, V alloy) that have been immersed in the liquid during the test period are not observed for oxidation / erosion and are equivalent to those that have not been treated.
During this test, the composition was clear and no fuming was observed.
Furthermore, the composition obtained by adding the additive of Example 4 to perfluoropolyether oil was stable even at room temperature, and no phase separation was observed after 168 hours.

Example 7
The same procedure as in Example 6 was repeated except that the time for the micro-oxidation test was increased to 48 hours. The weight loss was 1.46% by weight.

Example 8
The same procedure as in Example 6 was repeated using 0.5 g of the additive in Example 1. The weight loss after lapse of 24 hours at 300 ° C. was 0.98% by weight. Metals (stainless steel and Ti, Al, V alloy) that have been immersed in the liquid during the test period are not observed for oxidation / erosion and are equivalent to those that have not been treated.
The composition obtained by adding the additive of Example 1 to the perfluoropolyether oil was stable at room temperature and no phase separation was observed after 168 hours.

Example 9
The same procedure as in Example 8 was repeated except that the time for the micro oxidation test was increased to 48 hours. The weight loss was 1.6% by weight.

Example 10
The same procedure as in Example 8 was repeated except that the time for the micro oxidation test was increased to 72 hours. The weight loss was 2.2% by weight.

Example 11
The same as Example 6 was repeated using 0.5 g of the additive of Example 3. The weight loss after 24 hours at 300 ° C. was 0.47% by weight. Metals (stainless steel and Ti, Al, V alloy) that have been immersed in the liquid during the test period are not observed for oxidation / erosion and are equivalent to those that have not been treated.
The composition obtained by adding the additive of Example 3 to the perfluoropolyether oil was stable at room temperature and no phase separation was observed after 168 hours.

Example 12
The same as Example 6 was repeated using 0.5 g of the additive of Example 2. The weight loss after lapse of 24 hours at 300 ° C. was 0.82% by weight. Metals (stainless steel and Ti, Al, V alloy) that have been immersed in the liquid during the test period are not observed for oxidation / erosion and are equivalent to those that have not been treated.
The composition obtained by adding the additive of Example 2 to perfluoropolyether oil was stable at room temperature and no phase separation was observed after 168 hours.

Example 13 (comparative example)
The same thing as Example 6 was repeated without adding a stabilizer. White smoke was observed during the test. The oil after 24 hours at 300 ° C. was completely decomposed. During the test period, the metal (stainless steel and Ti, Al, V alloy) that had been immersed in the liquid was observed with obvious oxidation / erosion traces, and the surface was unusually dark.

Example 14 (comparative example)
The same procedure as in Example 6 was repeated except that 0.5 g of the non-triazine stabilizer represented by the formula 11 was used.

[Number average molecular weight of main chain is 1966, c / d is 1.2; manufactured according to the method described in Example 1 of European Patent 1,354,932. ]
The weight loss after 24 hours at 300 ° C. was 1.06% by weight. During the test period, the metal (stainless steel and Ti, Al, V alloy) that was immersed in the liquid was not observed or observed any traces of oxidation / erosion, and was equivalent to the untreated one.
However, the composition obtained by adding to the perfluoropolyether oil an additive having an aryl end group but not having a triazine ring as described in EP 1,354,932 is already in phase within 24 hours at room temperature. Separation occurred clearly.

Example 15 (comparative example)
The same procedure as in Example 6 was repeated except that 0.5 g of the stabilizer of Example 5 (Comparative Example) was used. The weight loss after lapse of 24 hours at 300 ° C. was 49% by weight.
Comparing the data relating to the stability of the examples according to the present invention with the above data, the compound having a triazine ring but not substituted with an aryl group is perfluorocarbon in an oxidizing environment in the presence of a metal at high temperature. It can be seen that the effect of stabilizing the polyether oil is insufficient.

Example 16
A lubricant containing 0.5 g of the additive of Example 2 and 9.5 g of a perfluoropolyether lubricant (commercial product: Fomblin® Y04) having a structure (1) with a kinematic viscosity at 20 ° C. of 40 cSt. An agent composition is prepared. This composition is diluted with 190 g of a fluorinated solvent (commercial product: Galden (registered trademark) SV90).
The metal sheet washed for the spray test is immersed in the diluent for 1 minute. Thereafter, the sheet is taken out and dried in a hot air dryer at 60 ° C. for 30 minutes to remove the solvent. The sheet is then placed in a nebulizer for testing.
After 118 hours from the start of the spray test, no traces of corrosion were found on the sheet.

Example 17 (comparative example)
The same as in Example 16 except that the additive of the present invention was not used and a lubricant obtained by mixing 10 g of the lubricating oil Fomblin (registered trademark) Y04 and 190 g of the fluorine-based solvent Galden (registered trademark) SV90 was used. Repeated that.
After 118 hours from the start of the spray test, corrosion was observed to spread in the range between 5% and 10% of the entire surface of the sheet.

Example 1 8
Same as Example 16 using a mixture of 0.5 g of additive of Example 2 and 199.5 g of fluorinated solvent (Galden® SV90) without using perfluoropolyether oil. Was repeated.
After 118 hours from the start of the spray test, no traces of corrosion were found on the sheet.

Example 19 (comparative example)
The same procedure as in Example 16 was repeated using only 200 g of a fluorinated solvent (Galden (registered trademark) SV90).
After 118 hours from the start of the spray test, corrosion was observed to spread over a range exceeding 10% of the entire surface of the sheet.

Claims (17)

A compound represented by formula (I) having at least one aryl triazine end group and containing a perfluoropolyether chain.

_[R f _{is, (CFXO), (CF 2} CF 2 O), (CF 2 CF 2 CF 2 O), (CF 2 CF 2 CF 2 CF 2 O), (CR 6 R 7 CF 2 CF 2 O) , (CF (CF ₃ ) CF ₂ O), (CF ₂ CF (CF ₃ ) O) (where X = F, CF ₃ ; R ₆ and R ₇ are H, Cl, or C 1-4, They are selected from perfluoroalkyl and may be the same or different from each other. } A (per) fluoropolyoxyalkylene chain having a statistical probability of 1 or 2 or more repeating units having the following structure in the main chain, and the number average molecular weight of R _f is 500 to 10,000;
W ₁ and W ₂ are —F or —CF ₃ and may be the same or different from each other;
T ₁ is —CHA _a —B _a (CH ₂ CH ₂ O) _na — {where A _a = H, CF ₃ ; B _a = O, S, NH; na is an integer of 0 to 6 and includes both ends. It is. };
T ₂ is —F, —CF ₃ , —C ₂ F ₅ , — (C ₂ F ₄ ) Cl, or

A group represented by:
Q ₁ and Q ₂ are each a perfluoropolyoxyalkylene chain having a structure of —T ₁ —CFW ₁ —O—R _f —CFW ₂ —T ^′ ₂ {T ^′ ₂ is —F, —CF ₃ , —C ₂ F ₅ , — (C ₂ F ₄ ) Cl; T ₁ , W ₁ and W ₂ have the same meaning as described above. }, Or

A group represented by {B is O, S, NH; R ₁ , R ₂ , R ₃ , R ₄ , R ₅ are H, F, NO ₂ , CN, linear or branched C ₁ -C ₈ perfluoroalkyl, carboxyl, phenyl (Ph), O-Ph, NH-Ph, S-Ph, which may be the same or different from each other. } And Q ₁ and Q ₂ may be the same or different from each other;
However, _{Q 1} and _{Q 2} are at least one of,

It is group shown by these. ] The compound according to claim 1, wherein the perfluoropolyether chain _Rf is selected from the structures of the formulas (A) to (F).
(A)
_{- (CF 2 CF (CF 3} ) O) a (CFXO) b -
Or _{- (CF 2 CF (CF 3} ) O) a (CFXO) b -CF 2 (R 'f) CF 2 -O- (CF 2 CF (CF 3) O) a (CFXO) b -
{In the formula (A), R _^'f is fluoro alkylene group having 1 to 4 carbon atoms; X is F or CF _3; a and b is an integer number average molecular weight is in the above range; a / b is between 10 and 100 and b is not 0. };
(B)
_{- (CF 2 CF 2 O)} c (CF 2 O) d (CF 2 (CF 2) z O) h -
{In formula (B), c, d and h are integers whose number average molecular weight is within the above range; c / d (d is not 0) is between 0.1 and 10; h / (c + d) ((c + d) is not 0) is between 0 and 0.05; z is 2 or 3; h may be 0. };
(C)
_{- (CF 2 CF (CF 3} ) O) e (CF 2 CF 2 O) f (CFXO) g -
{In Formula (C), X is F or CF ₃ ; e, f, g are integers whose number average molecular weight is within the above range; e / (f + g) is between 0.1 and 10 ; (F + g) is not 0: f / g is between 2 and 10. };
(D)
− (CF ₂ (CF ₂ ) _z O) _s −
{In formula (D), s is an integer giving the above molecular weight, and z has the meaning already defined. };
(E)
− (CR ₆ R ₇ CF ₂ CF ₂ O) _{j ′} −
Or _{- (CR 6 R 7 CF 2} CF 2 O) p '-R' f -O- (CR 6 R 7 CF 2 CF 2 O) q '-
{Wherein in (E), _{R 6} and _{R 7} are H, Cl, or selected from perfluoroalkyl having 1 to 4 carbon atoms, same or may be different from each other; R _^'f is from 1 to 4 carbon atoms And j ^′ , p ^′ , and q ^′ are integers having the above molecular weight. };
(F)
− (CF (CF ₃ ) CF ₂ O) _{j ″} −
{J ^″ in the formula (F) is an integer that gives the molecular weight.} The compound according to claim 2, wherein R _f is of the structure of formula (A) or formula (B).   Use of the compound according to any one of claims 1 to 3 as a heat stabilizer for fluorine oils and greases in a thermally oxidizing atmosphere in the presence of a metal.   Use of the compound according to any one of claims 1 to 3 as a rust inhibitor for fluorine oils and greases.   Use according to claim 4 as a rust inhibitor. A perfluoropolyether oil or a PFPE-based grease based on perfluoropolyether oil 99.95-90% by weight, and at least one triazine compound 0.05 of the structure of formula (1) according to claim 1-3 -10% by weight,
Lubricant composition containing The composition according to claim 7, wherein the perfluoropolyether oil is selected from the classification of formulas (1) to (8).
(1)
_{E-O- [CF 2 CF (} CF 3) O] m '(CFXO) n' -E '
[In the formula (1), X is —F or —CF ₃ ; E and E ^′ are selected from —CF ₃ , —C ₂ F ₅ or —C ₃ F ₇ and are the same or different from each other. M ^′ and n ^′ have a ratio of m ^′ / n ^′ between 20 and 1000, n ^′ is not 0, and a viscosity at 20 ° C. is between 10 cSt and 4,000 cSt. The repeating units are distributed with statistical probability in the main chain. ];
(2)
_{C 3 F 7 O- [CF (} CF 3) CF 2 O] o '-D
[In the formula (2), D is an _-C 2 _{F 5} or _-C 3 _{F 7;} o ^'is an integer such that the viscosity of the product is within the above reported range under (1). ];
(3)
_{{C 3 F 7 O- [CF} (CF 3) CF 2 O] p '-CF (CF 3) -} 2
[In formula (3), p ^′ is an integer whose viscosity falls within the range described in formula (1). ];
(4)
_{E-O- [CF 2 CF (} CF 3) O] q '(C 2 F 4 O) r' (CFX) s '-E'
[In the formula (4), X is —F or —CF ₃ ; E and E ^′ are selected from —CF ₃ , —C ₂ F ₅ or —C ₃ F ₇ and may be the same or different from each other; q ^′ , r ^′ and s ^′ are integers (including 0) whose viscosity falls within the range described in the formula (1). ];
(5)
_{E-O- (C 2 F 4} O) t '(CF 2 O) u' -E '
[In formula (5), E and E ^′ are selected from —CF ₃ , —C ₂ F ₅ or —C ₃ F ₇ and may be the same or different from each other; t ^′ and u ^′ are t ^′ / ^'it is between the ratio of 0.1 and 5, ^u' u is not zero, and the viscosity is an integer comprised within the range according to equation (1). ];
(6)
_{E-O- (CF 2 CF 2} CF 2 O) v '-E'
[In formula (6), E and E ^′ are selected from —CF ₃ , —C ₂ F ₅ or —C ₃ F ₇ and may be the same or different from each other; v ^′ may have a viscosity of formula (1) The number falls within the range described in. ];
(7)
_{D-O- (CF 2 CF 2} O) z '-D'
[D and D ^′ in the formula (7) are selected from —C ₂ F ₅ or —C ₃ F ₇ and may be the same or different from each other; z ^′ is the range described in the formula (1) An integer that is inside. ];
And (8)
_{E 1 -O (CF 2 O)} n (CF 2 CF 2 O) m - (CF 2 CF 2 CF 2 O) p (CF 2 CF 2 CF 2 CF 2 O) q -E 2
[In Formula (8), E ₁ and E ₂ are perfluoroalkyl end groups having a structure of — (CF ₂ ) _z CF ₃ , and z is an integer of 0 to 3, which may be the same or different from each other. N, m, p, q are integers whose viscosities fall within the range described in formula (1), m / n is between 2 and 20, n is not 0; (p + q) / ( The ratio of m + n + p + q) is between 0.05 and 0.2, (m + n + p + q) is not 0; n / (m + n + q + p) is in the range between 0.05 and 0.4, and (m + n + p + q) Is not 0. ]   The composition according to claim 8, wherein the perfluoropolyether oil is of any one of the formulas (1), (4), (5) and (8).   The composition according to any one of claims 7 to 9, comprising an additive usually used in perfluoropolyether lubricants. Stage A:
(I)
Perfluoropolyoxyalkylene derivative T ^″ ₁ -CFW ₁ —O—R _f —CFW ₂ —T ^” ₂ (II) represented by the formula (II)
[R _f , W ₁ and W ₂ have the same meaning as above; T ^″ ₁ and T ^″ ₂ may be the same or different from each other —CHA _a —B _a (CH ₂ CH ₂ O) _na —H Having structure {A _a = H, CF ₃ ; B _a = O, S, NH; na is an integer of 0 to 6 and includes a terminal. Or selected from F, CF ₃ , C ₂ F ₅ , (C ₂ F ₄ ) Cl; provided that at least one of the two terminals T ^″ ₁ and T ^″ ₂ is —CHA _a —B _a is a _{(CH 2 CH 2 O) na} -H. 〕When,
Trihalotriazine represented by the formula (III)

[J = Cl, F]
Equivalents of the compound of formula (II) in the presence of a solvent inert under the reaction conditions capable of dissolving the reactants at a temperature between 0 ° C. and 10 ° C. and an organic or inorganic base The ratio of the number to the number of moles of the compound represented by formula (III) is 1: 1,
(Ii)
The reaction product obtained in the above (i) and the compound represented by the formula (IV) are represented by QH (IV)
[Q is Q ₁ and Q ₂ described above. ]
React in a temperature range of 25-35 ° C.,
(Iii)
The reaction product obtained in the above (ii) and the compound represented by the formula (IV) (which may be the same as or different from that used in the above (ii)) may be in a temperature range of 65 to 100 ° C. React with
Stage B:
Separating the organic phase of the reaction mixture obtained in step A from the aqueous phase, then separating off any remaining organic or inorganic insoluble salts from the organic phase;
Stage C:
Washing the organic phase several times with an aqueous acid solution and then separating the compound having the structure of formula (I) from the organic solvent according to formula (1) according to any of claims 1-3 Process for producing the indicated triazine compound.   The production method according to claim 11, wherein the inert solvent in Step A is selected from toluene, xylene, hexafluoroxylene, acetone, and diethyl ketone. Are those inorganic base in step A is selected _NaOH, KOH, from _{Na 2 CO 3, K 2 CO} 3; organic base is 2,6-dimethylpyridine, 2-methylquinoline, 2,4,6-trimethylpyridine The manufacturing method in any one of Claims 11-12 which is selected from (collidine).   The production method according to any one of claims 11 to 13, wherein the base is 2,4,6-trimethylpyridine.   The ratio of the number of equivalents of base to the sum of the number of equivalents of compounds of formula (II) and formula (IV) used in the three steps of stage A is 1: 1 to 2: 1. The manufacturing method in any one of 11-14.   A lubricant grease having a perfluoropolyether base, comprising the additive according to claim 1, a perfluoropolyether oil, and a thickener. The grease according to claim 16, comprising talc, an inorganic filler, and an antiwear agent.